US11485715B2 - Method for producing N-(hydrocarbon)isocyanuric acid - Google Patents

Method for producing N-(hydrocarbon)isocyanuric acid Download PDF

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US11485715B2
US11485715B2 US17/434,803 US202017434803A US11485715B2 US 11485715 B2 US11485715 B2 US 11485715B2 US 202017434803 A US202017434803 A US 202017434803A US 11485715 B2 US11485715 B2 US 11485715B2
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isocyanuric acid
dihalogenated
hydrocarbon
group
producing
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US20220162175A1 (en
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Nobuyuki Kakiuchi
Tomohisa Utsunomiya
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/32—Cyanuric acid; Isocyanuric acid

Definitions

  • the present invention relates to a novel method for producing an N-(hydrocarbon)isocyanuric acid.
  • isocyanuric acid N-substituted product An N-substituted product of isocyanuric acid (hereinafter referred to as “isocyanuric acid N-substituted product”) has been used in a variety of fields including semiconductor fields (e.g., Patent Documents 1 and 2), and various synthesis methods for the isocyanuric acid N-substituted product have been reported for many years (e.g., Non-Patent Documents 1 to 3).
  • Patent Document 3 a method for producing an isocyanuric acid N-substituted product having one hydrocarbon group
  • a conventionally known production method for an isocyanuric acid N-substituted product having one alkyl group requires heating at a high temperature of 150° C. or higher for a long period of time, since isocyanuric acid has low solubility in an organic solvent.
  • the production method is not industrially useful, since high-temperature reaction causes a reduction in yield due to decomposition of a raw material and a product, and sequential reaction causes, for example, a reduction in yield and selectivity.
  • the use of a reagent of low boiling point at a high temperature requires a closed type high-pressure reaction apparatus. Meanwhile, low-temperature reaction requires an excessively large amount of an organic solvent for dissolution of isocyanuric acid, which causes problems in terms of poor volume efficiency and an increase in the amount of waste liquid.
  • Patent Document 3 which has been provided for solving such problems, requires multiple reaction steps, and has room for improvement from the viewpoints of, for example, cost reduction and time savings.
  • An object of the present invention is to provide a method for producing an isocyanuric acid N-substituted product suitable for industrial production. Specifically, an object of the present invention is to provide an industrially superior novel production method which requires neither multiple steps nor cumbersome treatment, and which enables selective production of an isocyanuric acid N-substituted product of interest in one pot.
  • an N-mono(hydrocarbon)isocyanuric acid (i.e., mono-substituted product) or an N-di(hydrocarbon)isocyanuric acid (i.e., di-substituted product) can be selectively produced at room temperature in one pot by reacting, in a solvent, at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate with a hydrocarbonization agent, such as at least one alkylating agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, preferably by mixing a solution or dispersion of a dihalogenated isocyanuric acid derivative
  • a first aspect of the present invention is a method for producing an N-(hydrocarbon)isocyanuric acid, the method comprising a step N of reacting, in a solvent, at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound.
  • a second aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the first aspect, wherein the step N comprises a step X of providing a solution or dispersion of at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate, and a step Y of mixing the solution or dispersion of the dihalogenated isocyanuric acid derivative with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, or comprises a step S of providing a solution or dispersion of at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sul
  • a third aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the second aspect, wherein the solution or dispersion of the dihalogenated isocyanuric acid derivative is an aqueous solution or an aqueous dispersion.
  • a fourth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the third aspect, wherein the aqueous solution or aqueous dispersion of the dihalogenated isocyanuric acid derivative contains water.
  • a fifth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to any one of the second to fourth aspects, wherein the step Y is a step of mixing the solution or dispersion of the dihalogenated isocyanuric acid derivative with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, and with a surfactant.
  • a sixth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the fifth aspect, wherein the surfactant contains at least one selected from the group consisting of a quaternary ammonium salt, a crown ether, and an alkylbenzenesulfonic acid salt.
  • a seventh aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to any one of the second to sixth aspects, wherein the step X is a step of providing a solution or dispersion containing at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate, and a base.
  • An eighth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the seventh aspect, wherein the base contains an inorganic base.
  • a ninth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the second aspect, wherein the solution or dispersion of the hydrocarbonization agent is an aqueous solution or an aqueous dispersion.
  • a tenth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the ninth aspect, wherein the aqueous solution or aqueous dispersion of the hydrocarbonization agent contains water.
  • An eleventh aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to any one of the second, ninth, or tenth aspect, wherein the step S is a step of providing a solution or dispersion containing at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, and a surfactant.
  • a twelfth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the eleventh aspect, wherein the surfactant contains at least one selected from the group consisting of a quaternary ammonium salt, a crown ether, and an alkylbenzenesulfonic acid salt.
  • a thirteenth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to any one of the second and ninth to twelfth aspects, wherein the step S is a step of providing a solution or dispersion containing at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, and a base.
  • a fourteenth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the thirteenth aspect, wherein the base contains an inorganic base.
  • a fifteenth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to any one of the first to fourteenth aspects, wherein the hydrocarbonization agent contains at least one selected from the group consisting of methyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl methanesulfonate, ethyl methanesulfonate, dimethyl sulfate, and diethyl sulfate.
  • a sixteenth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the fifteenth aspect, wherein the hydrocarbonization agent contains at least one selected from the group consisting of dimethyl sulfate and diethyl sulfate.
  • a seventeenth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to any one of the first to sixteenth aspects, wherein the dihalogenated isocyanuric acid derivative contains at least one selected from the group consisting of dichloroisocyanuric acid, sodium dichloroisocyanurate, and sodium dichloroisocyanurate dihydrate.
  • An eighteenth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to the seventeenth aspect, wherein the dihalogenated isocyanuric acid derivative contains sodium dichloroisocyanurate.
  • a nineteenth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to any one of the first to eighteenth aspects, wherein the amount of the hydrocarbonization agent is 0.3 mole equivalent to 4.0 mole equivalent relative to 1 mole equivalent of the dihalogenated isocyanuric acid derivative.
  • a twentieth aspect of the present invention is the method for producing an N-(hydrocarbon)isocyanuric acid according to any one of the first to nineteenth aspects, wherein the amount of the dihalogenated isocyanuric acid derivative is 0.03 to 0.3 times by mass that of the solvent used.
  • the present invention can provide an industrially useful production method which requires neither multiple steps nor cumbersome treatment, and which enables selective production of an N-(hydrocarbon)isocyanuric acid at room temperature in one pot with an eye on mass production.
  • the present invention is directed to a method for producing an N-(hydrocarbon)isocyanuric acid, the method including a step N of reacting, in a solvent, at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound.
  • the step N includes a step X of providing a solution or dispersion of at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate, and a step Y of mixing the solution or dispersion of the dihalogenated isocyanuric acid derivative with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, or includes a step S of providing a solution or dispersion of at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound, and a step T of mixing the solution or dispersion of the hydrocarbonization agent with at least
  • the solution or dispersion of the aforementioned dihalogenated isocyanuric acid derivative or hydrocarbonization agent is an aqueous solution or an aqueous dispersion.
  • the step N includes a step A of providing an aqueous solution or aqueous dispersion of at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate, and a step B of mixing the aqueous solution or the aqueous dispersion with a hydrocarbonization agent such as an alkylating agent.
  • a hydrocarbonization agent such as an alkylating agent
  • the step A is a step A1 of providing an aqueous solution of at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate.
  • the N-(hydrocarbon)isocyanuric acid according to the present invention refers to an isocyanuric acid (N-substituted product) having one or two hydrocarbon groups; specifically, a compound of the following Formula (1) (N-mono(hydrocarbon)isocyanuric acid) wherein one hydrocarbon group (substituent) is bonded to a nitrogen atom of isocyanuric acid, or a compound of the following Formula (2) (N-di(hydrocarbon)isocyanuric acid) wherein two hydrocarbon groups (substituents) are bonded to nitrogen atoms of isocyanuric acid.
  • Formula (1) N-mono(hydrocarbon)isocyanuric acid
  • Formula (2) N-di(hydrocarbon)isocyanuric acid
  • R is, for example, a C 1-10 hydrocarbon group.
  • the hydrocarbon group may be linear, branched, or cyclic, and may have at least one double bond or triple bond.
  • the hydrocarbon group is an alkyl group
  • the alkyl group is, for example, any of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n pentyl group, n nonyl group, n-decyl group, cyclohexylmethyl group, and cyclopentylmethyl group.
  • the hydrocarbon group other than the alkyl group include benzyl group, allyl group, and propargyl group.
  • Rs may be identical to or different from each other.
  • Rs are identical to each other from the viewpoint of efficient production of a target product.
  • This step involves reacting a dihalogenated isocyanuric acid derivative (i.e., starting material) with a hydrocarbonization agent in a solvent.
  • the aforementioned dihalogenated isocyanuric acid derivative refers to a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, or a dihalogenated isocyanuric acid salt hydrate.
  • These dihalogenated isocyanuric acid derivatives may be used alone or in combination of two or more species.
  • a single dihalogenated isocyanuric acid derivative is used, from the viewpoint of efficient production of a target product.
  • the dihalogenated isocyanuric acid may be, for example, a compound of the following Formula (3); the dihalogenated isocyanuric acid salt may be, for example, a compound of the following Formula (4); and the dihalogenated isocyanuric acid salt hydrate may be, for example, a compound of the following Formula (5).
  • Tautomers are shown in each of the following Formulae (3) to (5).
  • X 1 is a halogen atom and may be selected from among an iodine atom, a bromine atom, a chlorine atom, and a fluorine atom. In each of Formulae (3), (4), and (5), X 1 s may be identical to or different from each other.
  • M is an alkali metal and may be selected from among, for example, lithium, sodium, and potassium, and n is the number of hydrated water molecules.
  • the aforementioned dihalogenated isocyanuric acid derivatives of each type may be used alone or in combination of two or more species, and/or the dihalogenated isocyanuric acid derivatives of different types may be used in combination of two or more species.
  • a single derivative is used, from the viewpoint of efficient production of a target product.
  • dichloroisocyanuric acid, sodium dichloroisocyanurate, or sodium dichloroisocyanurate dihydrate is preferably used, from the viewpoint of industrial advantages, such as good solubility in water, etc., easy availability, and inexpensiveness.
  • the aforementioned dihalogenated isocyanuric acid derivative may be a commercially available product, or may be synthesized by, for example, any known method.
  • the dihalogenated isocyanuric acid derivative (e.g., dichloroisocyanuric acid derivative) synthesized by, for example, any known method may be used after isolation.
  • a reaction mixture containing the dihalogenated isocyanuric acid derivative may be used, as is, in the present invention without isolation.
  • isocyanuric acid may be reacted with a halogenating agent (e.g., sodium hypochlorite or chlorine) in a solvent, and the resultant reaction mixture containing one or more selected from among dichloroisocyanuric acid, sodium dichloroisocyanurate, and sodium dichloroisocyanurate dihydrate may be mixed with a hydrocarbonization agent described below.
  • a halogenating agent e.g., sodium hypochlorite or chlorine
  • a solvent No particular limitation is imposed on the aforementioned solvent, so long as it is used in this type of reaction and does not adversely affect the reaction.
  • Water, a buffer, and a water-soluble organic solvent are preferably used, from the viewpoints of, for example, production of a target product with high reproducibility, production of a target product at high yield, and workability.
  • a single solvent may be used, or two or more solvents may be used in combination.
  • the solvent used can be selected from among water, a buffer, and a water-soluble organic solvent.
  • the aforementioned buffer may be any known buffer depending on the target pH.
  • the buffer include buffers having buffering ability in a neutral region or a neutral to basic region, such as phosphate (e.g., disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, trisodium phosphate, and a mixture of any of these) buffer, ammonium formate buffer, and ammonium acetate buffer.
  • phosphate e.g., disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, trisodium phosphate, and a mixture of any of these
  • ammonium formate buffer e.g., ammonium formate buffer
  • ammonium acetate buffer e.g., ammonium formate buffer, and ammonium acetate buffer.
  • water-soluble organic solvent examples include, but are not limited to, alcohols, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, and 2-methoxypropanol; glycols, such as ethyl cellosolve, butyl cellosolve, ethylene glycol, and diethylene glycol; glycol ethers, such as propylene glycol monomethyl ether; ethers, such as tetrahydrofuran (THF); ketones, such as acetone; nitriles, such as acetonitrile; cyclic amides, such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); and sulfoxides, such as dimethyl sulfoxide (DMSO).
  • alcohols such as methanol, ethanol, n-propanol,
  • the aforementioned water-soluble organic solvent may be used in the form of a mixed solvent with water.
  • no particular limitation is imposed on the mixing ratio of water to the water-soluble organic solvent, so long as a homogeneous system can be maintained, for example, during provision (preparation) of an aqueous solution (aqueous dispersion) and after addition of a hydrocarbonization agent such as an alkylating agent described below.
  • the mixing ratio (by mass) of water to the water-soluble organic solvent is, for example, 0.1:99.9 to 99.9:0.1.
  • the water-soluble organic solvent may be used in combination with a slightly water-soluble organic solvent or a hydrophobic organic solvent (e.g., propylene glycol 1-monomethyl ether 2-acetate (PGMEA)), so long as the effects of the present invention are not impaired.
  • a slightly water-soluble organic solvent e.g., propylene glycol 1-monomethyl ether 2-acetate (PGMEA)
  • PMEA propylene glycol 1-monomethyl ether 2-acetate
  • the hydrocarbonization agent e.g., alkylating agent
  • a hydrocarbon group e.g., alkyl group
  • a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound may be collectively referred to as “hydrocarbonization agent.”
  • the halogenated hydrocarbon compound or the pseudo-halogenated hydrocarbon compound may be, for example, a compound of the following Formula (6).
  • R is a C 1-10 hydrocarbon group as shown in Formulae (1) and (2).
  • the hydrocarbon group may be linear, branched, or cyclic, and may have at least one double bond or triple bond.
  • X 2 is a halogen atom or a pseudo-halogen group.
  • the aforementioned halogen atom may be selected from among an iodine atom, a bromine atom, a chlorine atom, and a fluorine atom.
  • the compound of Formula (6) is a halogenated hydrocarbon compound.
  • the compound include, but are not limited to, methyl iodide, ethyl bromide, propyl bromide, allyl bromide, and propargyl bromide.
  • Examples of the aforementioned pseudo-halogen group include alkylsulfonyloxy groups, such as methanesulfonyloxy group; fluoroalkylsulfonyloxy groups, such as trifluoromethanesulfonyloxy group and nonafluorobutanesulfonyloxy group; and aromatic sulfonyloxy groups, such as benzenesulfonyloxy group and toluenesulfonyloxy group.
  • alkylsulfonyloxy groups such as methanesulfonyloxy group
  • fluoroalkylsulfonyloxy groups such as trifluoromethanesulfonyloxy group and nonafluorobutanesulfonyloxy group
  • aromatic sulfonyloxy groups such as benzenesulfonyloxy group and toluenesulfonyloxy group.
  • the compound of Formula (6) is a pseudo-halogenated hydrocarbon compound.
  • the compound include, but are not limited to, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, methyl methanesulfonate, and ethyl methanesulfonate.
  • dialkyl sulfate compound may be, for example, a compound of the following Formula (7).
  • R is a C 1-10 hydrocarbon group as shown in Formulae (1) and (2).
  • the hydrocarbon group may be linear, branched, or cyclic, and may have at least one double bond or triple bond.
  • two Rs may be identical to or different from each other.
  • Rs are identical to each other, from the viewpoint of efficient production of a target product.
  • dialkyl sulfate compound examples include dimethyl sulfate and diethyl sulfate.
  • the amount of the aforementioned hydrocarbonization agent (at least one selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound) to be used, so long as the effects of the present invention are not impaired.
  • the amount of the hydrocarbonization agent used is 0.3 mole equivalent to 4.0 mole equivalent relative to 1 mole equivalent of the dihalogenated isocyanuric acid derivative.
  • the amount of the aforementioned dihalogenated isocyanuric acid derivative is generally about 0.03 to 0.3 times by mass that of the solvent used.
  • the reaction temperature may be appropriately determined in consideration of, for example, the solvent used, the amount of the dihalogenated isocyanuric acid derivative, and the type and amount of the hydrocarbonization agent.
  • the reaction temperature is, for example, 0° C. to 70° C.
  • the reaction temperature is preferably 10° C. to 40° C., more preferably around ambient temperature (20° C. ⁇ 15° C.), from the viewpoints of, for example, efficient progress of the reaction, prevention of the decomposition or volatilization of a raw material used, and production of a target product with high reproducibility.
  • the aforementioned reaction may be performed in the presence of a base.
  • a base enables more selective production of an N-di(hydrocarbon)isocyanuric acid.
  • an inorganic base is used.
  • the inorganic base include alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide; alkali metal carbonates, such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates, such as calcium carbonate and magnesium carbonate; and alkali metal hydrogen carbonates, such as sodium hydrogen carbonate and potassium hydrogen carbonate.
  • alkali metal hydroxide is preferably used, and sodium hydroxide is particularly preferably used.
  • These inorganic bases may be used alone or in combination of two or more species.
  • the inorganic base used may be an anhydrate or a hydrate.
  • the amount of the aforementioned base used is preferably 0.5 mole equivalent to 3.0 mole equivalent relative to 1 mole equivalent of the dihalogenated isocyanuric acid derivative contained in the aforementioned solution (dispersion).
  • the base may be mixed with and dissolved in a solvent during mixing of the aforementioned dihalogenated isocyanuric acid derivative with the solvent.
  • the base may be added to and dissolved in the solvent before or after mixing of the dihalogenated isocyanuric acid derivative with the solvent.
  • the temperature at mixing (addition) or dissolution of the base may be appropriately adjusted (to, for example, room temperature (ambient temperature) to 50° C.) depending on the solubility of the base used.
  • the aforementioned reaction may be performed in the presence of a surfactant such as a phase transfer catalyst.
  • surfactant serving as a phase transfer catalyst examples include quaternary ammonium salts, such as benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetra-n-butylammonium bromide, and tetra-n-butylammonium hydrogen sulfate; quaternary phosphonium salts, such as tetraphenylphosphonium bromide; crown ethers, such as 12-crown-4 and 18-crown-6; and alkylbenzenesulfonic acid salts, such as sodium dodecylbenzenesulfonate.
  • quaternary ammonium salt can be used as a preferred phase transfer catalyst.
  • phase transfer catalysts may be used alone or in combination of two or more species.
  • the aforementioned surfactant e.g., phase transfer catalyst
  • the amount of the surfactant is generally 0.001 mole equivalent to 1.5 mole equivalent relative to 1 mole equivalent of the aforementioned dihalogenated isocyanuric acid derivative.
  • the aforementioned hydrocarbonization agent and an optionally used surfactant may optionally be dissolved or dispersed in a solvent, and may be used in the form of a solution or a dispersion.
  • the resultant target product can be isolated by a common method, and no particular limitation is imposed on the purification operation.
  • the solid precipitated after the reaction may be recovered through filtration, and the resultant solid may be washed with water or an aqueous solution of a reducing agent (e.g., sodium thiosulfate), followed by recrystallization in an organic solvent for an increase in purity.
  • a reducing agent e.g., sodium thiosulfate
  • phase separation using an organic solvent may be performed.
  • step N includes steps X and Y described below or steps S and T described below.
  • step N includes steps A and B described below.
  • Step X of Providing Solution or Dispersion of Dihalogenated Isocyanuric Acid Derivative or Step A of Providing Aqueous Solution or Aqueous Dispersion of Dihalogenated Isocyanuric Acid Derivative
  • This step involves providing a solution or dispersion of a dihalogenated isocyanuric acid derivative (i.e., starting material), or an aqueous solution or aqueous dispersion of the dihalogenated isocyanuric acid derivative; specifically, dissolving or dispersing the dihalogenated isocyanuric acid derivative in a solvent described below, to thereby provide (prepare) a solution or dispersion or aqueous solution or aqueous dispersion of the dihalogenated isocyanuric acid derivative used in the subsequent step B.
  • a dihalogenated isocyanuric acid derivative i.e., starting material
  • an aqueous solution or aqueous dispersion of the dihalogenated isocyanuric acid derivative specifically, dissolving or dispersing the dihalogenated isocyanuric acid derivative in a solvent described below
  • the solvent used for providing (preparing) the aqueous solution can be selected from among water, a buffer, and a water-soluble organic solvent. Specific examples and other conditions of the water and the water-soluble organic solvent are the same as those described above.
  • one or more solvents may be mixed with the aforementioned dihalogenated isocyanuric acid derivative, to thereby dissolve the derivative in the solvents.
  • one or more solvents may be mixed with isocyanuric acid and the aforementioned halogenating agent, to thereby provide (prepare) a reaction solvent containing the aforementioned dihalogenated isocyanuric acid derivative.
  • aqueous solution aqueous dispersion
  • water, a buffer, or a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent may be mixed with the aforementioned dihalogenated isocyanuric acid derivative, to thereby dissolve the derivative in, for example, water.
  • aqueous solution aqueous dispersion
  • water, a buffer, or a water-soluble organic solvent, or a mixed solvent of water or a buffer and a water-soluble organic solvent may be mixed with isocyanuric acid and the aforementioned halogenating agent, to thereby provide (prepare) a reaction aqueous solution containing the aforementioned dihalogenated isocyanuric acid derivative.
  • the temperature at mixing or dissolution may be appropriately determined depending on the solubility or dispersibility of the dihalogenated isocyanuric acid derivative or isocyanuric acid and the halogenating agent.
  • the temperature may be, for example, around ambient temperature (20° C. ⁇ 15° C.).
  • heating may be appropriately performed for dissolution. Since the dihalogenated isocyanuric acid derivative has high solubility in, for example, water, the aqueous solution can be generally provided (prepared) at room temperature (ambient temperature).
  • the solution (dispersion) or the aqueous solution (aqueous dispersion) may further contain a base.
  • the reaction system containing a base enables more selective production of an N-di(hydrocarbon)isocyanuric acid in steps Y and B described below. Specific examples of the base are the same as those described above.
  • the amount of the base used is preferably 0.5 mole equivalent to 3.0 mole equivalent relative to 1 mole equivalent of the dihalogenated isocyanuric acid derivative contained in the aforementioned solution (dispersion) or aqueous solution (aqueous dispersion).
  • the base When a base is used, no particular limitation is imposed on the order of mixing (addition) and dissolution of the base. Specifically, the base may be mixed with and dissolved in a solvent, water, a buffer, a water-soluble organic solvent, or a mixed solvent of water or a buffer and a water-soluble organic solvent during mixing of the aforementioned dihalogenated isocyanuric acid derivative. Alternatively, the base may be added to and dissolved in such a solvent before or after mixing of the dihalogenated isocyanuric acid derivative. When a base is used, a basic buffer containing, for example, ammonium acetate, ammonium formate, or aqueous ammonia may be used.
  • the temperature at mixing (addition) or dissolution of the base may be appropriately adjusted (to, for example, room temperature (ambient temperature) to 50° C.) depending on the solubility of the base used.
  • the step Y or B may be performed even when the dihalogenated isocyanuric acid derivative and the base (if used) are in the form of a partially dissolved solution.
  • the step Y or B is preferably performed after confirmation that the dihalogenated isocyanuric acid derivative and the base (if used) are completely dissolved in a solvent to form a homogeneous solution.
  • This step involves mixing the solution (dispersion) or aqueous solution (aqueous dispersion) obtained in the aforementioned step X or A with at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound.
  • at least one hydrocarbonization agent selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound.
  • hydrocarbonization agent the halogenated hydrocarbon compound, the pseudo-halogenated hydrocarbon compound, and the dialkyl sulfate compound are the same as those described above.
  • a surfactant e.g., phase transfer catalyst
  • specific examples of the surfactant are the same as those described above.
  • the surfactant e.g., phase transfer catalyst
  • the amount of the surfactant used is generally 0.001 mole equivalent to 1.5 mole equivalent relative to 1 mole equivalent of the dihalogenated isocyanuric acid derivative contained in the aforementioned solution (dispersion) or aqueous solution (aqueous dispersion).
  • the aforementioned hydrocarbonization agent (at least one selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound) and an optionally used surfactant may optionally be dissolved or dispersed in a solvent, and may be used in the form of a solution or a dispersion.
  • the solution (dispersion) or aqueous solution (aqueous dispersion) of the dihalogenated isocyanuric acid derivative provided in the aforementioned step X or A is mixed with the hydrocarbonization agent (at least one selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound) and an optionally used surfactant generally after the step X or A of providing the solution (dispersion) or aqueous solution (aqueous dispersion) of the dihalogenated isocyanuric acid derivative.
  • the hydrocarbonization agent at least one selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound
  • an optionally used surfactant generally after the step X or A of providing the solution (dispersion) or aqueous solution (aqueous dispersion) of the dihalogenated isocyanuric acid derivative
  • aqueous solution aqueous dispersion
  • hydrocarbonization agent e.g., the aforementioned alkylating agent
  • surfactant an optionally used surfactant
  • the hydrocarbonization agent e.g., the aforementioned alkylating agent
  • an optionally used surfactant are added to the aqueous solution (aqueous dispersion) provided in the step A without any treatment (e.g., without temperature adjustment).
  • the aqueous solution (aqueous dispersion) provided in the step A may be added to the hydrocarbonization agent (e.g., alkylating agent) and an optionally used surfactant (without, for example, temperature adjustment).
  • the reaction of producing an N-(hydrocarbon)isocyanuric acid proceeds in the reaction system.
  • an N-mono(hydrocarbon)isocyanuric acid is selectively produced
  • an N-di(hydrocarbon)isocyanuric acid is selectively produced.
  • the reaction temperature (the temperature in the reaction system) can be maintained at ambient temperature (20° C. ⁇ 15° C.) following the aforementioned step A, and may be appropriately adjusted (to, for example, room temperature (ambient temperature) to 50° C.) in consideration of, for example, the degree of progress of the reaction or the recovery procedure after production of an N-(hydrocarbon)isocyanuric acid.
  • the reaction of production of an N-(hydrocarbon)isocyanuric acid seems to proceed relatively easily even at room temperature (ambient temperature), and thus the reaction at room temperature (ambient temperature) is advantageous from the industrial viewpoint.
  • reaction time may vary depending on the type of the hydrocarbonization agent (at least one selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound) to be used, the presence or absence of a surfactant, and the type of the surfactant, and the reaction time is, for example, 0.1 hours to 10 hours.
  • the hydrocarbonization agent at least one selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound
  • the aforementioned hydrocarbonization agent at least one selected from the group consisting of a halogenated hydrocarbon compound, a pseudo-halogenated hydrocarbon compound, and a dialkyl sulfate compound
  • a surfactant no particular limitation is imposed on the order of addition (contact and mixing with the aqueous solution) of these materials.
  • the surfactant is first added (contacted and mixed with the aqueous solution), and then the hydrocarbonization agent is added, whereby the reaction can be caused to proceed uniformly.
  • the solid precipitated after the reaction may be recovered through filtration, and the resultant solid may be washed with water or an aqueous solution of a reducing agent (e.g., sodium thiosulfate), followed by recrystallization in an organic solvent or water and drying for an increase in purity.
  • a reducing agent e.g., sodium thiosulfate
  • phase separation using an organic solvent may be performed.
  • This step involves providing a solution (dispersion) or aqueous solution (aqueous dispersion) of a hydrocarbonization agent; specifically, dissolving or dispersing the hydrocarbonization agent in a solvent described above, to thereby provide (prepare) a solution, aqueous solution, or (aqueous) dispersion of the hydrocarbonization agent used in the subsequent step T.
  • hydrocarbonization agent used in the step S are the same as those described above.
  • one or more solvents may be mixed with the aforementioned hydrocarbonization agent, to thereby dissolve or disperse the hydrocarbonization agent in the solvents.
  • aqueous solution aqueous dispersion
  • water, a buffer, or a water-soluble organic solvent, or a mixed solvent of water or a buffer and a water-soluble organic solvent may be mixed with the aforementioned hydrocarbonization agent, to thereby dissolve or disperse the hydrocarbonization agent in, for example, water.
  • the temperature at mixing, dissolution, or dispersion may be appropriately determined depending on the solubility or dispersibility of the hydrocarbonization agent.
  • the temperature may be, for example, around ambient temperature (20° C. ⁇ 15° C.).
  • the solution (dispersion) or the aqueous solution (aqueous dispersion) may contain a surfactant (e.g., phase transfer catalyst) together with the aforementioned hydrocarbonization agent.
  • a surfactant e.g., phase transfer catalyst
  • Specific examples and conditions (e.g., amount to be used) of the surfactant used are the same as those described above.
  • the solution (dispersion) or the aqueous solution (aqueous dispersion) may further contain a base.
  • the reaction system containing a base enables more selective production of an N-di(hydrocarbon)isocyanuric acid in the step T described below.
  • Specific examples and conditions (e.g., amount to be used) of the base are the same as those described above.
  • hydrocarbonization agent and optionally used surfactant and base may optionally be dissolved or dispersed in a solvent, and may be used in the form of a solution or a dispersion.
  • the surfactant When a surfactant is used, no particular limitation is imposed on the order of mixing (addition), dissolution, and dispersion of the surfactant. Specifically, the surfactant may be mixed with and dissolved or dispersed in a solvent during mixing of the aforementioned hydrocarbonization agent. Alternatively, the surfactant may be added to and dissolved or dispersed in such a solvent before or after mixing of the hydrocarbonization agent.
  • the temperature at mixing is imposed on the temperature at mixing (addition), dissolution, or dispersion of the surfactant. Similar to the case of mixing, dissolution, or dispersion of the aforementioned hydrocarbonization agent, the temperature may be appropriately adjusted (to, for example, room temperature (ambient temperature) to 50° C.) depending on the solubility or dispersibility of the surfactant.
  • the base When a base is used, no particular limitation is imposed on the order of mixing (addition), dissolution, and dispersion of the base.
  • the base may be mixed with and dissolved or dispersed in a solvent, water, a buffer, a water-soluble organic solvent, or a mixed solvent of water and a water-soluble organic solvent during mixing of the aforementioned hydrocarbonization agent.
  • the base may be added to and dissolved or dispersed in such a solvent before or after mixing of the hydrocarbonization agent.
  • the temperature at mixing (addition), dissolution, or dispersion of the base may be appropriately adjusted (to, for example, room temperature (ambient temperature) to 50° C.) depending on the solubility of the base used.
  • the step T involves mixing the solution (dispersion) or aqueous solution (aqueous dispersion) of the hydrocarbonization agent provided in the step S with at least one dihalogenated isocyanuric acid derivative selected from the group consisting of a dihalogenated isocyanuric acid, a dihalogenated isocyanuric acid salt, and a dihalogenated isocyanuric acid salt hydrate.
  • the aforementioned dihalogenated isocyanuric acid derivative may be mixed in the form of a solid.
  • the dihalogenated isocyanuric acid derivative may optionally be dissolved or dispersed in a solvent, and may be used in the form of a solution or a dispersion.
  • the dihalogenated isocyanuric acid derivative is mixed in the form of a solid, the entirety of the derivative may be mixed at one time, or the derivative may be divided into small portions and mixed little by little.
  • an N-(hydrocarbon)isocyanuric acid can be more selectively produced.
  • the solution (dispersion) or aqueous solution (aqueous dispersion) provided in the aforementioned step S is mixed with the dihalogenated isocyanuric acid derivative generally after the step S of providing the solution (dispersion) or aqueous solution (aqueous dispersion) of the hydrocarbonization agent.
  • the dihalogenated isocyanuric acid derivative is added to the solution (dispersion) or aqueous solution (aqueous dispersion) provided in the step S without any treatment (e.g., without temperature adjustment).
  • the solution (dispersion) or aqueous solution (aqueous dispersion) provided in the step S may be added to the dihalogenated isocyanuric acid derivative (without, for example, temperature adjustment).
  • the reaction of producing an N-(hydrocarbon)isocyanuric acid proceeds in the reaction system.
  • an N-mono(hydrocarbon)isocyanuric acid is selectively produced
  • an N-di(hydrocarbon)isocyanuric acid is selectively produced.
  • the reaction temperature (the temperature in the reaction system) can be maintained at ambient temperature (20° C. ⁇ 15° C.) following the aforementioned step S, and may be appropriately adjusted (to, for example, room temperature (ambient temperature) to 50° C.) in consideration of, for example, the degree of progress of the reaction or the recovery procedure after production of an N-(hydrocarbon)isocyanuric acid.
  • the reaction of production of an N-(hydrocarbon)isocyanuric acid seems to proceed relatively easily even at room temperature (ambient temperature), and thus the reaction at room temperature (ambient temperature) is advantageous from the industrial viewpoint.
  • reaction time may vary depending on the type of the hydrocarbonization agent to be used, the presence or absence of a surfactant, and the type of the surfactant, and the reaction time is, for example, 0.1 hours to 10 hours.
  • HPLC LC-2010A HT System, available from SHIMADZU CORPORATION
  • liquid A acetonitrile for HPLC
  • liquid B 0.1% by mass aqueous phosphoric acid solution
  • Preparation of calibration curve of monomethylisocyanuric acid Firstly, 100 mg of standard monomethylisocyanuric acid was placed in a 50 mL measuring flask, and the flask was charged with acetonitrile to a predetermined volume. Subsequently, the resultant solution was removed from the flask with 5 mL, 10 mL, and 15 mL transfer pipettes, and each portion of the solution was added to a 50 mL measuring flask.
  • the thus-prepared three standard solutions were analyzed by HPLC, to thereby prepare a three-point internal standard calibration curve.
  • the calibration curve was used for quantification of monomethylisocyanuric acid.
  • Quantification of dimethylisocyanuric acid The molar sensitivity ratio of standard dimethylisocyanuric acid to standard monomethylisocyanuric acid was determined to be 1.93 under the present analytical conditions.
  • Dimethylisocyanuric acid was quantified by the following formula using the internal standard quantitative value of monomethylisocyanuric acid and the molar sensitivity ratio of dimethylisocyanuric acid.
  • Quantitative value of dimethylisocyanuric acid (the peak area of dimethylisocyanuric acid/the peak area of monomethylisocyanuric acid) ⁇ the internal standard quantitative value of monomethylisocyanuric acid/the molar sensitivity ratio (1.93)
  • Retention time trichloroisocyanuric acid: 1.5 min, sodium dichloroisocyanurate: 2.3 min, isocyanuric acid: 2.3 min, monomethylisocyanuric acid: 3.5 min, dimethylisocyanuric acid: 7.0 min, trimethylisocyanuric acid: 12.2 min, p-xylene: 16.0 min, monoethylisocyanuric acid: 3.7 min, diethylisocyanuric acid: 7.4 min, triethylisocyanuric acid: 12.3 min
  • a glass-made reaction container was charged with 5.23 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for six hours.
  • MMe-ICA monomethylisocyanuric acid
  • DMe-ICA dimethylisocyanuric acid
  • the reaction product was diluted with acetonitrile for HPLC (available from KANTO CHEMICAL CO., INC.) and pure water in a measuring flask, and the diluted product was sampled.
  • HPLC available from KANTO CHEMICAL CO., INC.
  • p-Xylene internal standard substance
  • a glass-made reaction container was charged with 5.23 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 0.09 g of tetramethylammonium chloride (available from Tokyo Chemical Industry Co., Ltd.) was added to the resultant solution, and then 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution.
  • sodium dichloroisocyanurate trade name: HILITE 60G, available from Nissan Chemical Corporation
  • the resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time.
  • MMe-ICA monomethylisocyanuric acid
  • DMe-ICA dimethylisocyanuric acid
  • a glass-made reaction container was charged with 5.23 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation), 0.94 g of sodium hydroxide (special grade, available from KANTO CHEMICAL CO., INC.), and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for two hours.
  • MMe-ICA monomethylisocyanuric acid
  • DMe-ICA dimethylisocyanuric acid
  • a glass-made reaction container was charged with 6.10 g of sodium dichloroisocyanurate dihydrate (trade name: HILITE 55G, available from Nissan Chemical Corporation) and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 4.51 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for six hours.
  • MMe-ICA monomethylisocyanuric acid
  • DMe-ICA dimethylisocyanuric acid
  • the reaction and the quantitative analysis were performed in the same manner as in Example 1, except that the reaction temperature was changed to 10° C., and the reaction time was changed to seven hours.
  • the reaction and the quantitative analysis were performed in the same manner as in Example 1, except that the reaction temperature was changed to 30° C., and the reaction time was changed to three hours.
  • a glass-made reaction container was charged with 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) and 30.0 g of water, and the resultant mixture was stirred at 20° C. for dispersion. Thereafter, 5.28 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) was added in a divided manner to the resultant dispersion over one hour. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for 2.5 hours.
  • MMe-ICA monomethylisocyanuric acid
  • DMe-ICA dimethylisocyanuric acid
  • a glass-made reaction container was charged with 3.07 g of isocyanuric acid (trade name: CA-P, available from Nissan Chemical Corporation) and 35.90 g of aqueous sodium hypochlorite solution (Cica first grade, available from KANTO CHEMICAL CO., INC.), and the resultant mixture was stirred at 40° C. for homogeneous dissolution, to thereby generate sodium dichloroisocyanurate in the reaction system. Thereafter, the resultant solution was cooled to 20° C., and 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the solution. The resultant mixture was stirred at 20° C. for six hours.
  • isocyanuric acid trade name: CA-P, available from Nissan Chemical Corporation
  • aqueous sodium hypochlorite solution Cica first grade, available from KANTO CHEMICAL CO., INC.
  • a glass-made reaction container was charged with 5.28 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) and 30.0 g of an organic solvent or a mixed solvent of an organic solvent and water shown in Table 4, and the resultant mixture was stirred at 20° C. Thereafter, 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred for six hours.
  • sodium dichloroisocyanurate trade name: HILITE 60G, available from Nissan Chemical Corporation
  • the reaction product was diluted with acetonitrile for HPLC (available from KANTO CHEMICAL CO., INC.) and pure water in a measuring flask, and the diluted product was sampled.
  • HPLC available from KANTO CHEMICAL CO., INC.
  • p-Xylene internal standard substance
  • a glass-made reaction container was charged with 5.28 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation), 0.05 g of tetra-n-butylammonium bromide (available from Tokyo Chemical Industry Co., Ltd.), and 30.0 g of water, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 5.32 g of methyl iodide (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C., and then solids of monomethylisocyanuric acid (MMe-ICA) and dimethylisocyanuric acid (DMe-ICA) were precipitated over time. The mixture containing the solids was stirred for six hours.
  • sodium dichloroisocyanurate trade name: HILITE 60G, available from Nissan Chemical Corporation
  • 0.05 g of tetra-n-butylammonium bromide available
  • a glass-made reaction container was charged with 5.28 g of sodium dichloroisocyanurate (trade name: HILITE 60G, available from Nissan Chemical Corporation) and 30.0 g of dimethylformamide, and the resultant mixture was stirred at 20° C. for homogeneous dissolution. Thereafter, 7.33 g of diethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant solution. The resultant mixture was stirred at 20° C. for six hours.
  • sodium dichloroisocyanurate trade name: HILITE 60G, available from Nissan Chemical Corporation
  • diethyl sulfate available from Tokyo Chemical Industry Co., Ltd.
  • the reaction was performed by the method of Example 11, and then filtration was performed at ambient temperature, to thereby recover 4.65 g of a wet product containing MMe-ICA.
  • the wet product was placed in a glass-made reaction container, and 3.50 g of methanol (special grade, available from KANTO CHEMICAL CO., INC.) and 28.0 g of water were added to the container, followed by heating to 95° C. Subsequently, 5.0 g of toluene (special grade, available from KANTO CHEMICAL CO., INC.) was added to the resultant mixture for phase separation and recovery of the aqueous phase. This operation was repeated twice. Thereafter, the aqueous phase was cooled to 5° C.
  • the MMe-ICA crystal was diluted with acetonitrile for HPLC in a measuring flask, and relative area (%) was analyzed by HPLC.
  • the relative areas (%) of monomethylisocyanuric acid (MMe-ICA), dimethylisocyanuric acid (DMe-ICA), trimethylisocyanuric acid (TMe-ICA), and others were 98.5%, 0.5%, 0.7%, and 0.3%, respectively.
  • the reaction was performed by the method of Example 7, and then the resultant reaction mixture was cooled to 10° C. and subjected to filtration, to thereby recover 5.03 g of a wet product containing DMe-ICA.
  • the wet product was placed in a glass-made reaction container, and 20 g of water was added to the container, followed by heating to 50° C. Thereafter, the resultant product was cooled to 10° C., and 4.76 g of a precipitated wet product containing a larger amount of DMe-ICA was recovered through filtration. The same operation was repeated again, and 4.61 g of a wet product containing a larger amount of DMe-ICA was recovered through filtration.
  • the wet product was placed in a glass-made reaction container, and 15 g of methanol (special grade, available from KANTO CHEMICAL CO., INC.) was added to the container, followed by heating to 60° C. Thereafter, the resultant mixture was cooled to 10° C., and 2.12 g of a precipitated wet product containing a larger amount of DMe-ICA was recovered through filtration. The resultant wet product was dried under reduced pressure, to thereby yield 2.03 g of a DMe-ICA crystal.
  • the DMe-ICA crystal was diluted with acetonitrile for HPLC in a measuring flask, and relative area (%) was analyzed by HPLC.
  • MMe-ICA monomethylisocyanuric acid
  • DMe-ICA dimethylisocyanuric acid
  • TMe-ICA trimethylisocyanuric acid
  • a glass-made reaction container was charged with 3.07 g of isocyanuric acid (trade name: CA-P, available from Nissan Chemical Corporation), 0.95 g of sodium hydroxide (special grade, available from KANTO CHEMICAL CO., INC.), and 30.0 g of water, and the resultant mixture was stirred at 20° C. However, homogeneous dissolution failed to be achieved. Thereafter, 6.00 g of dimethyl sulfate (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise to the resultant slurry. The resultant mixture was stirred at 20° C. for two hours.
  • isocyanuric acid trade name: CA-P, available from Nissan Chemical Corporation
  • sodium hydroxide special grade, available from KANTO CHEMICAL CO., INC.
  • 6.00 g of dimethyl sulfate available from Tokyo Chemical Industry Co., Ltd.

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